Sulphonated carboxylic amide



Patented Oct. 24, 1933 1,9324%": SULPHONATEDY CARBOXYLIC AMIDE The present 1 Fritz Guenther, Ludwigshafen-on-the-Rhine,

and Hans Haussmann, Mannheim, Germany, assignors to I. G. Farbenindustrie Aktien-- gesellschaft, Frankfort-on-the -Main, Germany No Drawing. Application August 31, 1931, Serial No. 560,512, and in Great Britain August 7,

13 Claims.

nvention relates to the production of assistants for the textile and allied industries, such as wetting, cleansing and dispersing agents.

In the copending application Ser. No. 441,717, filed April 4, 1930, the present inventors and another have described a process for the production of assistants for the textile and allied industries, such as wetting, cleansing and dispersing agents, by converting organic carboxylic acids into amides and ucts if they are phuric, ester radicles.

acids have been sulphonating the resulting prodfree from sulphonic acid or sul- Thus 'for example fatty condensed with taurine to form the amide of the fatty acid concerned with the aminoethane sulphonic acid.

We have now found that valuable assistants for the textile and allied industries, such as wetting, cleansing and dispersing agents, are obtained by causing carboxylic acid anhydrides or halides to react acid substances, salts, in the pre with aminomethane sulphonici. e. the free acids and their sence of an alkaline diluent the said components being so chosen that the sum of the carbon atoms in aliphatic chains thereof is at least six.

Anhydrides o r halides of carboxylic acids which are suitable for the purposes according to the present invention may be chosen for example from those of saturated or unsaturated fatty acids, such as those of the series from acetic to stearic acids, or hon atoms, of r acids containing even more car esinic and naphthenic acids, of

mixtures of carboxylic acids obtained by the destructive oxidation of paraffin waxes, mineral oils, middle wax, of mixed oils and the like, of acids of montan aliphatic-aromatic carboxylic acids, such as of the type of phenyl-stearic or dodecyl'benzoic acids or other alkylated aroaromatic carboxylic acids, such as benzoic acid or naphthoic acid. The said carboxylic acid anhydrides or halides may also contain substituents,

such as halogen,

nitro, amino or hydroxy groups.

As aminomethane sulphonic acid substances are intended aminomethane sulphonic acid (H2NCH2-SO3H) or ,a salt thereof and derivatives of these compounds containing at least one hydrogen atom connected to the nitrogen atom as for example the conversion products from bisulphite compou described in the nds of formaldehyde (which are literature in part as sulphurous acid esters) with ammonia or amines of aliphatic, aliphatic for example me -aromatic or aromatic nature as thyl, butyl, cetyl, cyclohexyl or also in lower or higher quantities. If desired the at the reaction temperatures.

benzyl amines, aniline or toluidine, and also products containing the grouping in which R-CO defines the acyl radicle of a carboxylic acid, Y defines hydrogen or an organic radicle, preferably an alkyl radicle, especially an aliphatic hydrocarbon radicle, and X defines hydrogen or the salt forming portion of an alkaline, metal-or nitrogenous base, such as K or Na or ammonia-pyridine, dimethyl aniline or alkylol so amines such asfethanol amines, which latter salts may be obtained from the salts directly obtained by the usual conversion reactions. In any case the sum of the number of carbon atoms in CH2- RCON/ should be at least six, the components employed in the amidification being chosen correspondingly asmentioned above; if R-CO be for example CH3CH2CO, Y is at least CH3-CH2.

The reaction is carried out in the presence of alkaline diluents, such as water containing an alkali as for example sodium or potassium hydroxides, or organic tertiary bases, such as pyridine, dimethyl aniline or triethylamine and the like, preferably in equimolecular quantities or said organic bases may be employed as such in N0 the absence of water provided they are liquid In all cases the said alkaline diluents serve as acid-binding agents and combine with the acids set free during the reaction. As a rule, in the presence of water, low temperatures i. e. those below 35 C. are employed, temperatures between 15 and 25 C. being usual- 1y preferred. If anhydrides of the carboxylic acids be employed the products will contain the corresponding salts of the acids with the base employed and may be freed therefrom for example by means of an aqueous pulp of gypsum whereby the carboxylic acids are precipitated. In most cases, especially if anhydrides of the acids of vegetal, i. e. animal or vegetable, oils or fats have been employed, the soaps formed may be left in the products.

The carboxylic amides obtained have a high stability to alkalines and acids and are not precipitated from aqueous solutions by the substances forming the hardness of water. They are even stable to alkalies when heated, while boiling with strong mineral acids may lead to partial saponification. The products have a very high wetting, cleansing and emulsifying power and may therefore be advantageously employed in many branches of daily and industrial use. They may be employed with especial advantage in the textile, leather and paper industries; they are suitable for cleansing, levelling, softening and penetrating, and also as assistants for many other improving treatments and as emulsifying and dispersing agents for emulsifying or dispers-' ing water-insoluble substances such as fats, oils, waxes, hydrocarbons and the like, in water or aqueous solutions.

The amides may be employed for these purposes as such or in admixture with each other or together with other substances, such as soaps or saponaceous substances, bleaching agents, such as perborates or percarbonates, salts as for example Glaubers salt, sodium carbonate or bicarbonate, waterglass and like water-soluble salts, organic solvents such as trichlorethylene, benzyl alcohol or ethylene glycol mono-cresyl ether, glycerol, higher aliphatic alcohols such as from hexyl to cetyl alcohols and like solvents.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by Weight.

Example 1 40 parts of a methylaminomethane sulphonic acid (CI-IaNH-CH2-SO3H) obtainable by the interaction of formaldehyde-bisulphite with methylamine, are dissolved in 250 parts of water and 60 parts of the chlorides of the acids of coconut oil are added thereto. 60 parts of an aqueous caustic soda solution of 40 B. strength are caused to flow into the mixture at from 15 to 20 C. while cooling and stirring well. After stirring for some time, 410 parts of an approximately 20 per cent paste of the reaction product are obtained. This is soluble in water to give a clear solution and has a very high stability, at room temperature, to acids and to alkaline agents and is not precipitated from its aqueous solutions by the substances forming the hardness of water.

The reaction proceeds according to the equation the acids of coconut oil being calculated as C11H23COOH.

10 parts of a 20 per cent paste of the coconut oil acid amide of methylaminomethane sulphonic acid are dissolved in 1000 parts of water. A solution having an extremely high wetting power is obtained which is also capable of scouring 20 parts of suint wool within A hourat from 40 to 50 C; the solution may be employed for washing further batches of suintwool.

40 parts of aminomethane sulphonic acid are dissolved in 250 parts of water while adding aqueous caustic soda solution until the solution is slightly alkaline, whereupon 50 parts of palmitic acid chloride are added at from 20 to 25 C. and the reaction mixture is kept alkaline by adding aqueous caustic soda solution. The reaction mixture is stirred for from 3 to 4 hours and then allowed to settle. A paste is obtained which constitutes an efficient softening agent for artificial silk such as viscose of cuprammonium silk. In the place of the palmitic chloride other carboxylic acid halides, such as halides of naphthenic acids may be employed.

The reaction proceeds according to the equation If palmitic anhydride be employed the product comprises, besides the amide, an equivalent quantity of palmitic sodium salt.

Example 3 40 parts of an aminomethane sulphonic acid are dissolved in 250 parts of water while adding aqueous caustic soda solution until the solution is slightly alkaline, whereupon 50 parts of oleic acid chloride are added at from 20 to 25 C. and the reaction mixture is kept alkaline by adding aqueous caustic soda solution. The reaction mixture is stirred for from 3 to 4 hours. A product is obtained which is a highly efficient agent for washing piece goods. Instead of oleic chloride, oleic anhydride may be employed.

The reaction proceeds according to the equation in which R.CO is the acyl radicle of a carboxylic acid, Y is hydrogen or a hydrocarbon radicle, X is hydrogen or the salt forming portion of an alkaline, metal or nitrogenous base, and in which amides the group contains at least six carbon atoms.

2. A sulphonated carboxylic amide corresponding to the general formula Y in which R-CO is the acyl radicle of a carboxylic acid, Y is hydrogen or a hydrocarbon radicle, X is hydrogen or the salt forming portion of an alkaline, metal or nitrogenous base, and in which amides the group contains at least six carbon atoms.

3. A sulphonated carboxylic amide corresponding to the general formula in which R-CO is the acyl radicle of a carboxylic acid, Y is hydrogen or an aliphatic hydrocarbon radicle, X is hydrogen'or the salt forming portionof an alkaline, metal or nitrogenous base, and in which amides the group contains at least six carbon atoms.

4. A sulphonated carboxylic amide corresponding to the general formula CHPSOSX 11-0 0-N in which RCO is the acyl radicle of an aliphatic carboxylic acid, Y is hydrogen or a hydrocarbon radicle, X is hydrogen or the salt forming portion of an alkaline, metal or nitrogenous base, and in which amides the group contains at least six carbon atoms.

5. A sulphonated carboxylic amide corresponding to the general formula cH,- s0=x R-C ON in which R-CO is the acyl radicle of a fatty acid, Y is hydrogen or a hydrocarbon radicle, X is hydrogen or the saltforming portion of an alkaline, metal or nitrogenous base, and in which amides the group /CH2- 'R-OO-N contains at least six carbon atoms.

6. A sulphonated carboxylic amide corresponding to the general formula cnrsoax R-CON Y in which R-CO is the acyl radicle of a fatty acid of vegetal oils or fats, Y is hydrogen or an aliphatic hydrocarbon and X is hydrogen or the salt forming portion of an alkaline, metal or nitrogenous base.

'7. A sulphonated carboxylic amide corresponding to the general formula GET-503 R-CON in which H0 is the acyl radicle of a fatty acid of a vegetable oil or fat, Y is hydrogen or an aliphatic hydrocarbon and Xis hydrogen or the salt forming portion of an alkaline, metal or nitrogenous base.

8. A sulphonated carboxylic amide corresponding to the general formula in which RCO is the acyl radicle of an unsaturated fatty acid of a vegetable oil or fat, Y is hydrogen or an aliphatic hydrocarbon and X is hydrogen or the salt forming portion of an alkaline, metal or nitrogenous base.

9. Asulphonated carboxylic amide corresponding to the general formula CHz-SO X in which R--CO is the acyl radicle of a saturated fatty acid of a vegetable oil or fat, Y is hydrogen or CH3 and X is hydrogen or the salt forming portion of an alkaline, metal or nitroge- 12. The process for the production of sulphonated carboxylic amides which comprises acting with an agent selected from the group consisting of carboxylic halides and anhydrides on an aminomethane sulphonic acid, containing at least one hydrogen atom connected to the nitrogen atom, in the presence of an alkaline diluent, care I being taken that the sum of carbon atoms in said carboxylic 'halides or anhydrides and in said aminomethane sulphonic acid is at least six.

v 13. A sulphonated carboxylic amide corre-- sponding to the formula in which R-CO denotes the acyl radicles of the acids of coconut oil and X stands for hydrogen or the salt forming portion of an alkaline, metal or nitrogenous base.

FRITZ GUENTHER. HANS HZUSBMAN'N. 

